EP1492744B1 - Method for colouring fertilisers - Google Patents

Method for colouring fertilisers Download PDF

Info

Publication number
EP1492744B1
EP1492744B1 EP03712015A EP03712015A EP1492744B1 EP 1492744 B1 EP1492744 B1 EP 1492744B1 EP 03712015 A EP03712015 A EP 03712015A EP 03712015 A EP03712015 A EP 03712015A EP 1492744 B1 EP1492744 B1 EP 1492744B1
Authority
EP
European Patent Office
Prior art keywords
pigments
pigment
weight
pigment preparation
fertilizer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP03712015A
Other languages
German (de)
French (fr)
Other versions
EP1492744A1 (en
Inventor
Andreas Harz
Olaf Müller
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Clariant Produkte Deutschland GmbH
Original Assignee
Clariant Produkte Deutschland GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Clariant Produkte Deutschland GmbH filed Critical Clariant Produkte Deutschland GmbH
Publication of EP1492744A1 publication Critical patent/EP1492744A1/en
Application granted granted Critical
Publication of EP1492744B1 publication Critical patent/EP1492744B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05GMIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G3/00Mixtures of one or more fertilisers with additives not having a specially fertilising activity
    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05GMIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G5/00Fertilisers characterised by their form
    • C05G5/30Layered or coated, e.g. dust-preventing coatings
    • CCHEMISTRY; METALLURGY
    • C05FERTILISERS; MANUFACTURE THEREOF
    • C05GMIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G5/00Fertilisers characterised by their form
    • C05G5/30Layered or coated, e.g. dust-preventing coatings
    • C05G5/38Layered or coated, e.g. dust-preventing coatings layered or coated with wax or resins

Definitions

  • the present invention is a process for coloring fertilizers with pigments.
  • Fertilizer mixtures are colored with inorganic pigment powders containing small amounts of an oil.
  • the oil is used for dedusting the finely divided inorganic pigment powder.
  • the present invention has for its object to provide a method for coloring fertilizers, wherein a high color strength, light fastness and hiding power is achieved, which is ecotoxicologically flawless and has high acid and alkali resistance in the application medium.
  • the addition to the application medium should not be limited by solubility limits.
  • the present invention is a process for coloring fertilizers, characterized in that a pigment preparation of 5 to 60 wt .-% of at least one pigment, 40 to 95 wt .-% of a paraffin oil and / or vegetable oil, 0 to 10 wt .-% of a dispersant or dispersant mixture and 0 to 5 wt .-% of conventional additives, each based on the total weight of the pigment preparation produces, optionally the pigment preparation with paraffin oil and / or vegetable oil diluted, and the pigment preparation or the diluted pigment preparation applied to the fertilizer to be colored.
  • a pigment preparation which contains from 5 to 40% by weight of at least one organic pigment and from 60 to 95% by weight of a paraffin oil and / or vegetable oil.
  • a pigment preparation is used which contains 10 to 60% by weight of at least one inorganic pigment and 40 to 90% by weight of a paraffin oil and / or vegetable oil.
  • a pigment preparation which consists of 10 to 35 wt .-%, in particular 15 to 25 wt .-%, of at least one organic pigment, 65 to 90 wt .-%, in particular 75 to 85 wt .-%, of a Paraffin oil and / or vegetable oil, 0 to 10 wt .-% of a dispersant or dispersant mixture, and 0 to 5 wt .-% of conventional additives.
  • organic pigments in the context of the invention are monoazo pigments, disazo pigments, disazo condensation pigments, laked azo pigments, triphenylmethane pigments, thioindigo pigments, thiazine indigo pigments, perylene pigments, perinone pigments, anthanthrone pigments, diketopyrrolopyrrole pigments, dioxazine pigments, quinacridone pigments, Phthalocyanine pigments, isoindolinone pigments, isoindoline pigments, benzimidazolone pigments, naphthol pigments and quinophthalone pigments. Particularly noteworthy are acidic to alkaline carbon blacks from the group Furnaceruße or gas blacks.
  • inorganic pigments for the purposes of the invention are white pigments, iron oxide pigments, iron blue pigments, chromium oxide pigments, ultramarine pigments, mixed phase pigments, sulfide / sulfide selenide pigments, carbonate pigments, chromate / chromate molybdate pigments, complex salt pigments, silicate pigments, luster pigments, luminescent pigments.
  • paraffin oil is understood as meaning a low-viscosity mixture of saturated aliphatic hydrocarbons having a density of between 0.82 and 0.89 g / ml and a dynamic viscosity (at 25 ° C.) of between 25 and 80 mPas.
  • Commercially available paraffin oils, also known as white oils, which are suitable for the process according to the invention can still contain up to 40% of aromatic hydrocarbons.
  • Vegetable oils for the purposes of the present invention, are liquid commercial oils derived from oilseeds, such as e.g. Sunflower oil, olive oil, palm kernel oil, rapeseed oil, and mixtures of such oils understood.
  • fertilizers are predominantly mineral artificial fertilizers, such as e.g. Nitrogen, phosphate, potash, lime, and magnesium fertilizers which may be mixed with organic fertilizers and / or trace elements understood.
  • mineral artificial fertilizers such as e.g. Nitrogen, phosphate, potash, lime, and magnesium fertilizers which may be mixed with organic fertilizers and / or trace elements understood.
  • fertilizers that can be colored according to the process of the invention are: ammonium sulfate, ammonium nitrate, calcium ammonium nitrate, urea, urea-aldehyde condensates, nitrogen magnesia, ammonium sulfate nitrate, calcium nitrate, calcium cyanamide, superphosphate, double, triple superphosphate, Thomas flour, Thomas phosphate, dicalcium phosphate, Potassium chloride, potassium sulfate, kalimagnesia, calcium carbonate, calcium oxide, as well as Mixtures thereof.
  • the said fertilizers may also be enveloped with organic polymers or sulfur. Suitable dispersants are anionic, cationic and nonionic surface-active compounds.
  • alkyl sulfates alkyl sulfonates, alkyl phosphates, alkylbenzenesulfonates such as lauryl sulfate, stearyl sulfate, dodecylsulfonates, octadecylsulfates, dodecylsulfonates, condensation products of fatty acid and taurine or hydroxyethanesulfonic acid, alkoxylation products of alkylphenols, castor oil rosin esters, fatty alcohols, fatty amines, fatty acids, and fatty acid amides, reaction products of nonylphenol and shorter-chain, substituted Alkylphenols and their polymeric derivatives, such as formaldehyde condensation products and
  • Suitable additives include emulsifiers, anti-settling agents, anti-caking agents, wetting agents, preservatives, viscosity stabilizers and additives which influence the rheology.
  • anti-caking agents in particular those are used which prevent the caking of the fertilizer granules.
  • the pigment preparation used according to the invention can be prepared by dispersing the organic or inorganic pigment in the form of a powder, flush paste, pressed cake or granules in the presence of the said oils and optionally dispersants and / or customary additives. If dispersants and / or additives are added, these components are preferably first mixed with the oil, the pigment stirred and, depending on the grain hardness of the pigment used with stirrers, dissolvers, rotor-stator mills, ball mills, stirred ball mills, such as sand and bead mills, Fast mixers, kneading apparatus or High performance bead mills dispersed. The resulting pigment preparation is optionally further diluted with the said oil. Depending on the desired color intensity, the dilution can vary within wide limits, for example down to 1: 100.
  • the above-described pigment preparation is expediently in an amount of 0.00001 to 0.10 wt .-%, preferably 0.001 to 0.015 wt .-%, in particular 0.005 to 0 , 01 wt .-%, based on the weight of the fertilizer to be colored, applied to the fertilizer.
  • This can be achieved, for example, by spraying the pigment preparation with a suitable device, such as e.g. a spraying or spraying machine.
  • the pigment preparation can also be applied directly to the surface of the artificial fertilizer.
  • the temperature of the oil and the pigment preparation may conveniently be between 10 and 80 ° C.
  • oil-containing pigment preparations can also be used for the pigmentation of shoe polish, candles, wax crayons, putty, cosmetics, paint and dispersion paints, dispersion varnishes, for printing inks, for example textile printing, flexographic or gravure printing inks, for wallpaper paints, for wood protection systems, for viscose spin dyeing , for paints, for sausage casings, for Seeds, for glass bottles, for the mass coloration of roof tiles, for plasters, for wood stains, for pulp, for colored pencil leads, felt pens, ink, pastes for pens, chalks, detergents and cleaners, shoe care products, coloring of latex products, abrasives and for coloring of plastics and high molecular weight materials, and as colorants in electrophotographic toners and developers, such as one- or two-component powder toners, magnetic toners, liquid toners, polymerization toners and other specialty toners, as colorants in ink-jet inks, especially those on a non-com
  • the sprayed amount varied depending on the desired color intensity between 1 and 1000 g of pigment preparation per tonne of fertilizer.

Abstract

The invention relates to a method for colouring fertilisers, characterised in that a pigment-preparation containing 5 - 60 wt.- % of at least one pigment, 40 - 95 wt.- % of a paraffin oil and/or vegetable oil, 0 10 wt.- % of a dispersing agent or dispersing agent mixture and 0 - 5 wt.- % usual additives is produced, each of the percentages being in relation to the total weight of the pigment preparation; the pigment-preparation is optionally diluted with paraffin oil and/or vegetable oil and the pigment preparation or the diluted pigment-preparation is applied to the fertiliser which is to be coloured.

Description

Gegenstand der vorliegenden Erfindung ist ein Verfahren zum Einfärben von Düngemitteln mit Pigmenten.The present invention is a process for coloring fertilizers with pigments.

Zur Kennzeichnung von Düngemitteln ist eine Vielzahl von Farbstoffen, Farbstofflösungen oder Dispersionen bekannt. Häufig werden Solvent Farbstoffe verwendet, die in Öl gelöst dem Düngemittel zugesetzt werden. Solvent Farbstoffe weisen jedoch eine geringe Lichtechtheit und Farbstärke auf. Die Säure- und Alkalibeständigkeit ist schlecht. Es besteht eine Löslichkeitsgrenze des Farbstoffes in ÖI, womit eine niedrige Farbtiefe einher geht. Auch eine erhöhte Deckkraft wäre wünschenswert.For the characterization of fertilizers a variety of dyes, dye solutions or dispersions is known. Frequently, solvent dyes are used which are dissolved in oil and added to the fertilizer. Solvent dyes, however, have a low light fastness and color strength. The acid and alkali resistance is poor. There is a solubility limit of the dye in oil, which is accompanied by a low color depth. Also, an increased opacity would be desirable.

In der WO 97/19030 werden Düngemittelgemische mit anorganischen Pigmentpulvern, die geringe Mengen eines Öls enthalten, eingefärbt. Das Öl dient zum Entstauben der feinteiligen anorganischen Pigmentpulver.In the WO 97/19030 Fertilizer mixtures are colored with inorganic pigment powders containing small amounts of an oil. The oil is used for dedusting the finely divided inorganic pigment powder.

Der vorliegenden Erfindung lag die Aufgabe zugrunde, ein Verfahren zum Einfärben von Düngemitteln bereitzustellen, wobei eine hohe Farbstärke, Lichtechtheit und Deckkraft erzielt wird, das ökotoxikologisch einwandfrei ist und im Anwendungsmedium eine hohe Säure- und Alkalibeständigkeit aufweist. Außerdem sollte die Zudosierung zum Anwendungsmedium nicht durch Löslichkeitsgrenzen limitiert sein.The present invention has for its object to provide a method for coloring fertilizers, wherein a high color strength, light fastness and hiding power is achieved, which is ecotoxicologically flawless and has high acid and alkali resistance in the application medium. In addition, the addition to the application medium should not be limited by solubility limits.

Es wurde gefunden, dass eine Pigment-Präparation eines organischen oder anorganischen Pigments in einem Öl überraschenderweise die gestellten Anforderungen in hohem Maße erfüllt.It has been found that a pigment preparation of an organic or inorganic pigment in an oil surprisingly satisfies the stated requirements to a high degree.

Gegenstand der vorliegenden Erfindung ist ein Verfahren zum Einfärben von Düngemitteln, dadurch gekennzeichnet, dass man eine Pigment-Präparation aus 5 bis 60 Gew.-% mindestens eines Pigments, 40 bis 95 Gew.-% eines Paraffinöls und/oder Pflanzenöls, 0 bis 10 Gew.-% eines Dispergiermittels oder Dispergiermittelgemisches und 0 bis 5 Gew.-% üblicher Zusatzstoffe, jeweils bezogen auf das Gesamtgewicht der Pigment-Präparation, herstellt, gegebenenfalls die Pigment-Präparation mit Paraffinöl und/oder Pflanzenöl verdünnt, und die Pigment-Präparation oder die verdünnte Pigment-Präparation auf das einzufärbende Düngemittel aufbringt.The present invention is a process for coloring fertilizers, characterized in that a pigment preparation of 5 to 60 wt .-% of at least one pigment, 40 to 95 wt .-% of a paraffin oil and / or vegetable oil, 0 to 10 wt .-% of a dispersant or dispersant mixture and 0 to 5 wt .-% of conventional additives, each based on the total weight of the pigment preparation produces, optionally the pigment preparation with paraffin oil and / or vegetable oil diluted, and the pigment preparation or the diluted pigment preparation applied to the fertilizer to be colored.

In einer besonderen Ausführungsform des erfindungsgemäßen Verfahrens setzt man eine Pigment-Präparation ein, die 5 bis 40 Gew.-% mindestens eines organischen Pigments und 60 bis 95 Gew.-% eines Paraffinöls und/oder Pflanzenöls enthält.
In einer weiteren Ausführungsform des erfindungsgemäßen Verfahrens setzt man eine Pigment-Präparation ein, die 10 bis 60 Gew.-% mindestens eines anorganischen Pigmentes und 40 bis 90 Gew.-% eines Paraffinöls und/oder Pflanzenöls enthält.
In a particular embodiment of the process according to the invention, a pigment preparation is used which contains from 5 to 40% by weight of at least one organic pigment and from 60 to 95% by weight of a paraffin oil and / or vegetable oil.
In a further embodiment of the method according to the invention, a pigment preparation is used which contains 10 to 60% by weight of at least one inorganic pigment and 40 to 90% by weight of a paraffin oil and / or vegetable oil.

Vorzugsweise wird eine Pigment-Präparation eingesetzt, die aus 10 bis 35 Gew.-%, insbesondere 15 bis 25 Gew.-%, mindestens eines organischen Pigments, 65 bis 90 Gew.-%, insbesondere 75 bis 85 Gew.-%, eines Paraffinöls und/oder Pflanzenöls, 0 bis 10 Gew.-% eines Dispergiermittels oder Dispergiermittelgemisches, sowie 0 bis 5 Gew.-% üblicher Zusatzstoffe besteht. Vorzugsweise wird weiterhin eine Pigment-Präparation eingesetzt, die aus 15 bis 50 Gew.-%, insbesondere 20 bis 40 Gew.-%, eines anorganischen Pigmentes, 50 bis 85 Gew.-%, insbesondere 60 bis 80 Gew.-%, eines Paraffinöls und/oder Pflanzenöls, 0 bis 10 Gew.-% eines Dispergiermittels oder Dispergiermittelgemisches, und 0 bis 5 Gew.-% üblicher Zusatzstoffe besteht.Preferably, a pigment preparation is used, which consists of 10 to 35 wt .-%, in particular 15 to 25 wt .-%, of at least one organic pigment, 65 to 90 wt .-%, in particular 75 to 85 wt .-%, of a Paraffin oil and / or vegetable oil, 0 to 10 wt .-% of a dispersant or dispersant mixture, and 0 to 5 wt .-% of conventional additives. Preference is furthermore given to using a pigment preparation which comprises from 15 to 50% by weight, in particular from 20 to 40% by weight, of an inorganic pigment, from 50 to 85% by weight, in particular from 60 to 80% by weight Paraffin oil and / or vegetable oil, 0 to 10 wt .-% of a dispersant or dispersant mixture, and 0 to 5 wt .-% of conventional additives.

Beispiele für organische Pigmente im Sinne der Erfindung sind Monoazopigmente, Disazopigmente, Disazokondensationspigmente, verlackte Azopigmente, Triphenylmethanpigmente, Thioindigopigmente, Thiazinindigopigmente, Perylenpigmente, Perinonpigmente, Anthanthronpigmente, Diketopyrrolopyrrolpigmente, Dioxazinpigmente, Chinacridonpigmente, Phthalocyaninpigmente, Isoindolinonpigmente, Isoindolinpigmente, Benzimidazolonpigmente, Naphtholpigmente und Chinophthalonpigmente. Insbesondere zu nennen sind saure bis alkalische Ruße aus der Gruppe Furnaceruße oder Gasruße.Examples of organic pigments in the context of the invention are monoazo pigments, disazo pigments, disazo condensation pigments, laked azo pigments, triphenylmethane pigments, thioindigo pigments, thiazine indigo pigments, perylene pigments, perinone pigments, anthanthrone pigments, diketopyrrolopyrrole pigments, dioxazine pigments, quinacridone pigments, Phthalocyanine pigments, isoindolinone pigments, isoindoline pigments, benzimidazolone pigments, naphthol pigments and quinophthalone pigments. Particularly noteworthy are acidic to alkaline carbon blacks from the group Furnaceruße or gas blacks.

Beispiele für anorganische Pigmente im Sinne der Erfindung sind Weißpigmente, Eisenoxidpigmente, Eisenblaupigmente, Chromoxidpigmente, Ultramarinpigmente, Mischphasenpigmente, Sulfid-/Sulfidselenidpigmente, Carbonatpigmente, Chromat-/ Chromat-Molybdatpigmente, Komplexsalzpigmente, Silicatpigmente, Glanzpigmente, Leuchtpigmente.Examples of inorganic pigments for the purposes of the invention are white pigments, iron oxide pigments, iron blue pigments, chromium oxide pigments, ultramarine pigments, mixed phase pigments, sulfide / sulfide selenide pigments, carbonate pigments, chromate / chromate molybdate pigments, complex salt pigments, silicate pigments, luster pigments, luminescent pigments.

Unter Paraffinöl wird im Sinne der vorliegenden Erfindung ein dünnflüssiges Gemisch gesättigter aliphatischer Kohlenwasserstoffe mit einer Dichte zwischen 0,82 und 0,89 g/ml und einer Dynamischen Viskosität (bei 25°C) zwischen 25 und 80 mPas verstanden. Handelsübliche Paraffinöle, auch Weißöle genannt, die für das erfindungsgemäße Verfahren in Betracht kommen, können noch bis zu 40 % aromatische Kohlenwasserstoffe enthalten.For the purposes of the present invention, paraffin oil is understood as meaning a low-viscosity mixture of saturated aliphatic hydrocarbons having a density of between 0.82 and 0.89 g / ml and a dynamic viscosity (at 25 ° C.) of between 25 and 80 mPas. Commercially available paraffin oils, also known as white oils, which are suitable for the process according to the invention can still contain up to 40% of aromatic hydrocarbons.

Unter Pflanzenölen werden im Sinne der vorliegenden Erfindung flüssige handelsübliche Öle aus Ölsaaten, wie z.B. Sonnenblumenöl, Olivenöl, Palmkernöl, Rapsöl, sowie Mischungen solcher Öle verstanden.Vegetable oils, for the purposes of the present invention, are liquid commercial oils derived from oilseeds, such as e.g. Sunflower oil, olive oil, palm kernel oil, rapeseed oil, and mixtures of such oils understood.

Unter Düngemitteln werden im Sinne der vorliegenden Erfindung überwiegend mineralische Kunstdünger, wie z.B. Stickstoff-, Phosphat-, Kali-, Kalk-, und Magnesium-Dünger, die mit organischen Düngern und/oder Spurenelementen vermischt sein können, verstanden.For the purposes of the present invention, fertilizers are predominantly mineral artificial fertilizers, such as e.g. Nitrogen, phosphate, potash, lime, and magnesium fertilizers which may be mixed with organic fertilizers and / or trace elements understood.

Beispiele für Düngemittel, die nach dem erfindungsgemäßen Verfahren eingefärbt werden können, sind: Ammoniumsulfat, Ammoniumnitrat, Kalkammonsalpeter, Harnstoff, Harnstoff-Aldehyd-Kondensate, Stickstoffmagnesia, Ammonsulfatsalpeter, Kalksalpeter, Calciumcyanamid, Superphosphat, Doppel-, Tripelsuperphosphat, Thomasmehl, Thomasphosphat, Dicalciumphosphat, Kaliumchlorid, Kaliumsulfat, Kalimagnesia, Calciumcarbonat, Calciumoxid, sowie Gemische davon. Die genannten Düngemittel können auch mit organischen Polymeren oder Schwefel umhüllt sein.
Als Dispergiermittel eignen sich anionische, kationische und nichtionische grenzflächenaktive Verbindungen. Besonders bewährt haben sich Dispergiermittel, die eine oder mehrere mittel- oder langkettige Kohlenwasserstoffketten besitzen. Von der Vielzahl der Verbindungen soll an dieser Stelle nur eine Auswahl aufgeführt werden, ohne jedoch die Anwendbarkeit der erfindungsgemäßen Verbindungen auf diese Beispiele einzuschränken. Beispiele sind Alkylsulfate, Alkylsulfonate, Alkylphosphate, Alkylbenzolsulfonate wie Laurylsulfat, Stearylsulfat, Dodecylsulfonate, Octadecylsulfate, Dodecylsulfonate, Kondensationsprodukte aus Fettsäure und Taurin oder Hydroxyethansulfonsäure, Alkoxylierungsprodukte von Alkylphenolen, Ricinusölkolophoniumestern, Fettalkoholen, Fettaminen, Fettsäuren, und Fettsäureamiden, Umsetzungsprodukte aus Nonylphenol und kürzerkettigen, substituierten Alkylphenolen sowie deren polymeren Derivaten, z.B. Formaldehyd-Kondensationsprodukten sowie polymere Verbindungen wie z.B. Polyacrylate und deren Oxalkylate.
Examples of fertilizers that can be colored according to the process of the invention are: ammonium sulfate, ammonium nitrate, calcium ammonium nitrate, urea, urea-aldehyde condensates, nitrogen magnesia, ammonium sulfate nitrate, calcium nitrate, calcium cyanamide, superphosphate, double, triple superphosphate, Thomas flour, Thomas phosphate, dicalcium phosphate, Potassium chloride, potassium sulfate, kalimagnesia, calcium carbonate, calcium oxide, as well as Mixtures thereof. The said fertilizers may also be enveloped with organic polymers or sulfur.
Suitable dispersants are anionic, cationic and nonionic surface-active compounds. Have proven particularly dispersing agents which have one or more medium or long chain hydrocarbon chains. Of the large number of compounds, only a selection should be made at this point, but without restricting the applicability of the compounds according to the invention to these examples. Examples are alkyl sulfates, alkyl sulfonates, alkyl phosphates, alkylbenzenesulfonates such as lauryl sulfate, stearyl sulfate, dodecylsulfonates, octadecylsulfates, dodecylsulfonates, condensation products of fatty acid and taurine or hydroxyethanesulfonic acid, alkoxylation products of alkylphenols, castor oil rosin esters, fatty alcohols, fatty amines, fatty acids, and fatty acid amides, reaction products of nonylphenol and shorter-chain, substituted Alkylphenols and their polymeric derivatives, such as formaldehyde condensation products and polymeric compounds such as polyacrylates and their alkoxylates.

Als übliche Zusatzstoffe kommen Emulgatoren, Antiabsetzmittel, Antibackmittel, Netzmittel, Konservierungsmittel, Viskositätsstabilisatoren und Additive, welche die Rheologie beeinflussen, in Betracht. Als Antibackmittel werden insbesondere solche eingesetzt, die das Zusammenbacken der Düngemittelkörnchen verhindern.Suitable additives include emulsifiers, anti-settling agents, anti-caking agents, wetting agents, preservatives, viscosity stabilizers and additives which influence the rheology. As anti-caking agents, in particular those are used which prevent the caking of the fertilizer granules.

Die erfindungsgemäß verwendete Pigment-Präparation kann hergestellt werden, indem das organische oder anorganische Pigment in Form eines Pulvers, Flushpaste, Presskuchens oder Granulats in Gegenwart der genannten Öle und gegebenenfalls Dispergiermittel und/oder üblicher Zusatzstoffe dispergiert wird. Falls Dispergiermittel und/oder Zusatzstoffe zugegeben werden, werden diese Komponenten vorzugsweise zunächst mit dem Öl vermischt, das Pigment eingerührt und je nach Kornhärte des eingesetzten Pigments mit Rührwerken, Dissolvern, Rotor-Stator-Mühlen, Kugelmühlen, Rührwerkskugelmühlen, wie Sand- und Perlmühlen, Schnellmischern, Knetapparaturen oder Hochleistungsperlmühlen dispergiert. Die erhaltene Pigment-Präparation wird gegebenenfalls mit dem genannten Öl weiter verdünnt. Die Verdünnung kann je nach gewünschter Farbintensität in weiten Grenzen schwanken, beispielsweise bis auf 1:100.The pigment preparation used according to the invention can be prepared by dispersing the organic or inorganic pigment in the form of a powder, flush paste, pressed cake or granules in the presence of the said oils and optionally dispersants and / or customary additives. If dispersants and / or additives are added, these components are preferably first mixed with the oil, the pigment stirred and, depending on the grain hardness of the pigment used with stirrers, dissolvers, rotor-stator mills, ball mills, stirred ball mills, such as sand and bead mills, Fast mixers, kneading apparatus or High performance bead mills dispersed. The resulting pigment preparation is optionally further diluted with the said oil. Depending on the desired color intensity, the dilution can vary within wide limits, for example down to 1: 100.

Zur erfindungsgemäßen Einfärbung des Düngemittels wird die vorstehend beschriebene Pigmentpräparation, gegebenenfalls nach vorheriger Verdünnung mit dem genannten Öl, zweckmäßigerweise in einer Menge von 0,00001 bis 0,10 Gew.-%, bevorzugt 0,001 bis 0,015 Gew.-%, insbesondere 0,005 bis 0,01 Gew.-%, bezogen auf das Gewicht des einzufärbenden Düngemittels, auf das Düngemittel appliziert. Dies kann beispielsweise durch Versprühen der Pigmentpräparation mit einer geeigneten Vorrichtung, wie z.B. einer Sprüh- oder Spritzmaschine, erfolgen. Die Pigmentpräparation kann aber auch direkt auf die Oberfläche des Kunstdüngers appliziert werden.For dyeing the fertilizer according to the invention, the above-described pigment preparation, optionally after prior dilution with said oil, is expediently in an amount of 0.00001 to 0.10 wt .-%, preferably 0.001 to 0.015 wt .-%, in particular 0.005 to 0 , 01 wt .-%, based on the weight of the fertilizer to be colored, applied to the fertilizer. This can be achieved, for example, by spraying the pigment preparation with a suitable device, such as e.g. a spraying or spraying machine. The pigment preparation can also be applied directly to the surface of the artificial fertilizer.

Sowohl bei der Verdünnung als auch bei der Applikation kann die Temperatur des Öls sowie der Pigment-Präparation zweckmäßigerweise zwischen 10 und 80°C liegen.Both in the dilution and in the application, the temperature of the oil and the pigment preparation may conveniently be between 10 and 80 ° C.

Bei Verwendung der beschriebenen ölhaltigen Pigment-Präparation erzielt man eine deutlich höhere Deckkraft, eine höhere Lichtechtheit, höhere Farbstärken, sowie ökologische Vorteile gegenüber Farbstoffen (da diese in der Regel kennzeichnungspflichtig sind), und eine deutlich bessere Säure- und Alkalibeständigkeit. Außerdem ist eine direkte Einarbeitung auf das Endprodukt möglich, wobei auf den Löseprozess verzichtet werden kann. Das Herstellen von Mischfarben ist im kalten Zustand möglich, da es sich um flüssige Präparationen handelt.When using the described oil-containing pigment preparation to achieve a significantly higher hiding power, higher light fastness, higher color strengths, as well as ecological advantages over dyes (since these are usually subject to labeling), and a significantly better acid and alkali resistance. In addition, a direct training on the final product is possible, which can be dispensed with the dissolution process. The production of mixed colors is possible in the cold state, since they are liquid preparations.

Ölhaltige Pigment-Präparationen können prinzipiell auch für die Pigmentierung von Schuhcreme, Kerzen, Wachsmalstiften, Knetmasse, Kosmetika, Anstrich- und Dispersionsfarben, Dispersionslacken, für Druckfarben, beispielsweise Textildruck-, Flexodruck- oder Tiefdruckfarben, für Tapetenfarben, für Holzschutzsysteme, für Viskose-Spinnfärbung, für Lacke, für Wurstdärme, für Saatgut, für Glasflaschen, für die Massefärbung von Dachziegeln, für Putze, für Holzbeizen, für Papiermassen, für Buntstiftminen, Faserschreiber, Tuschen, Pasten für Kugelschreiber, Kreiden, Wasch- und Reinigungsmittel, Schuhpflegemittel, Einfärbung von Latex-Produkten, Schleifmitteln sowie zum Einfärben von Kunststoffen und hochmolekularen Materialien, sowie als Farbmittel in elektrophotographischen Tonern und Entwicklern, wie z.B. Ein- oder Zweikomponentenpulvertonern, Magnettonern, Flüssigtonern, Polymerisationstonern sowie weiteren Spezialtonern, als Farbmittel in Ink-Jet-Tinten, insbesondere solchen auf nicht-wässriger Basis, Hot-melt- und Mikroemulsionstinten, eingesetzt werden.In principle, oil-containing pigment preparations can also be used for the pigmentation of shoe polish, candles, wax crayons, putty, cosmetics, paint and dispersion paints, dispersion varnishes, for printing inks, for example textile printing, flexographic or gravure printing inks, for wallpaper paints, for wood protection systems, for viscose spin dyeing , for paints, for sausage casings, for Seeds, for glass bottles, for the mass coloration of roof tiles, for plasters, for wood stains, for pulp, for colored pencil leads, felt pens, ink, pastes for pens, chalks, detergents and cleaners, shoe care products, coloring of latex products, abrasives and for coloring of plastics and high molecular weight materials, and as colorants in electrophotographic toners and developers, such as one- or two-component powder toners, magnetic toners, liquid toners, polymerization toners and other specialty toners, as colorants in ink-jet inks, especially those on a non-aqueous basis, hot-melt melted and microemulsion inks used.

BeispieleExamples

In den nachstehenden Beispielen wurde ein Weißöl folgender Spezifikation verwendet: Kinematische Viskosität bei 20°C: 32 mm2 /s Dichte bei 20°C: 848 kg/m3 Fließpunkt: -9°C Brechungsindex bei 20°C: 1,466 Kohlenwasserstoffverteilung: Paraffinisch 67 % Aromatisch 33 % In the examples below, a white oil of the following specification was used: Kinematic viscosity at 20 ° C: 32 mm 2 / s Density at 20 ° C: 848 kg / m 3 Pour point: -9 ° C Refractive index at 20 ° C: 1,466 Hydrocarbon distribution: Paraffinic 67% Aromatic 33%

Beispiel 1:Example 1:

25 Teile C.I. Pigment Red 112 sowie 75 Teile Weißöl wurden bei 30 bis 40°C mittels einer Perlmühle (Fa. Drais) mit 280 Teilen Zirkonoxidperlen (d = 1 mm) über mehrere Passagen gemahlen. Die Pigmentpräparation hat eine hohe Farbstärke mit sehr reinem Farbton, erweist sich gut fließfähig sowie als lagerstabil, d.h. die Probe bleibt trotz der Warmlagerung für 5 Wochen bei 50°C gut fließfähig.25 parts C.I. Pigment Red 112 and 75 parts of white oil were ground at 30 to 40 ° C by means of a bead mill (Drais) with 280 parts zirconium oxide beads (d = 1 mm) over several passages. The pigment preparation has a high color strength with a very pure color, proves to be readily flowable and storage stable, i. the sample remains well flowable for 5 weeks at 50 ° C despite the warm storage.

Weitere Beispiele für Pigmentpräparationen:

  • 2) 27 Teile Pigment Yellow 13 und 73 Teile Weißöl
  • 3) 10 Teile Pigment Yellow 154 und 90 Teile Weißöl
  • 4) 20 Teile Pigment Red 53:1 und 80 Teile Weißöl
  • 5) 17 Teile Pigment Red 57:1 und 83 Teile Weißöl
  • 6) 50 Teile Pigment Red 101 und 50 Teile Weißöl
  • 7) 24 Teile Pigment Red 112 und 1,5 Teile Polyethylenwachs und 74,5 Teile Weißöl
  • 8) 15 Teile C.I. Pigment Blue 15 und 85 Teile Weißöl
  • 9) 20 Teile Pigment Blue 15:1 und 80 Teile Weißöl
  • 10) 20 Teile Pigment Green 7 und 80 Teile Weißöl
  • 11) 20 Teile Pigment Black 7 und 80 Teile Weißöl
Further examples of pigment preparations:
  • 2) 27 parts of Pigment Yellow 13 and 73 parts of white oil
  • 3) 10 parts of Pigment Yellow 154 and 90 parts of white oil
  • 4) 20 parts Pigment Red 53: 1 and 80 parts white oil
  • 5) 17 parts Pigment Red 57: 1 and 83 parts white oil
  • 6) 50 parts Pigment Red 101 and 50 parts white oil
  • 7) 24 parts Pigment Red 112 and 1.5 parts polyethylene wax and 74.5 parts white oil
  • 8) 15 parts CI Pigment Blue 15 and 85 parts white oil
  • 9) 20 parts of Pigment Blue 15: 1 and 80 parts of white oil
  • 10) 20 parts Pigment Green 7 and 80 parts white oil
  • 11) 20 parts Pigment Black 7 and 80 parts white oil

Die in den Beispielen 1 bis 11 beschriebenen Pigmentpräparationen wurden mit Weißöl 1:10 verdünnt und mittels einer Sprühapparatur auf einen handelsüblichen NPK-Kunstdünger appliziert:The pigment preparations described in Examples 1 to 11 were diluted 1:10 with white oil and applied by means of a spray apparatus to a commercially available NPK synthetic fertilizer:

Die versprühte Menge variierte je nach gewünschter Farbintensität zwischen 1 und 1000 g Pigment-Präparation je Tonne Düngemittel.The sprayed amount varied depending on the desired color intensity between 1 and 1000 g of pigment preparation per tonne of fertilizer.

Claims (10)

  1. A method for coloring fertilizers, which comprises the production of a pigment preparation comprising 5 to 60% by weight of at least one pigment, 40 to 95% by weight of a paraffin oil and/or vegetable oil, 0 to 10% by weight of a dispersant or dispersant mixture and 0 to 5% by weight of conventional additives, in each case based on the total weight of the pigment preparation, the optional dilution of the pigment preparation with paraffin oil and/or vegetable oil, and the application of the pigment preparation or diluted pigment preparation to the fertilizer to be colored.
  2. The method as claimed in claim 1, wherein the pigment preparation comprises 5 to 40% by weight of at least one organic pigment and 60 to 95% by weight of a paraffin oil and/or vegetable oil.
  3. The method as claimed in claim 1, wherein the pigment preparation comprises 10 to 60% by weight of at least one inorganic pigment and 40 to 90% by weight of a paraffin oil and/or vegetable oil.
  4. The method as claimed in at least one of claims 1 to 3, wherein the pigment is an organic pigment from the group consisting of monoazo pigments, diazo pigments, diazo condensation pigments, laked azo pigments, triphenylmethane pigments, thio indigo pigments, thiazine-indigo pigments, perylene pigments, perinone pigments, anthanthrone pigments, diketopyrrolopyrrole pigments, dioxazine pigments, quinacridone pigments, phthalocyanine pigments, isoindolinone pigments, isoindoline pigments, benzimidazolone pigments, naphthol pigments, quinophthalone pigments, furnace blacks and gas blacks.
  5. The method as claimed in at least one of claims 1 to 3, wherein the pigment is an inorganic pigment from the group consisting of white pigments, iron oxide pigments, iron blue pigments, chromium oxide pigments, ultramarine pigments, mixed phase pigments, sulfide/sulfide selenide pigments, carbonate pigments, chromate/chromate-molybdate pigments, complex salt pigments, silicate pigments, luster pigments and luminescent pigments.
  6. The method as claimed in at least one of claims 1 to 5, wherein the fertilizer is a synthetic inorganic fertilizer from the group consisting of nitrogen, phosphate, potassium, calcium and magnesium fertilizers.
  7. The method as claimed in at least one of claims 1 to 6, wherein a suspension agent, anticaking agent, wetting agent, preservative, viscosity stabilizer and/or additive for influencing the rheology is used as conventional additive.
  8. The method as claimed in at least one of claims 1 to 7, wherein the pigment, in the form of a powder or granular material, is dispersed in the presence of the paraffin oil and/or vegetable oil and optionally of the dispersant and/or of the conventional additives.
  9. The method as claimed in at least one of claims 1 to 8, wherein the pigment preparation or the diluted pigment preparation is applied to the fertilizer in an amount of 0.00001 to 0.10% by weight, based on the weight of the fertilizer to be colored.
  10. The method as claimed in claim 9, wherein the pigment preparation or the diluted pigment preparation is sprayed onto the surface of the fertilizer.
EP03712015A 2002-04-03 2003-03-14 Method for colouring fertilisers Expired - Lifetime EP1492744B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10214591 2002-04-03
DE10214591A DE10214591A1 (en) 2002-04-03 2002-04-03 Process for coloring fertilizers
PCT/EP2003/002675 WO2003082776A1 (en) 2002-04-03 2003-03-14 Method for colouring fertilisers

Publications (2)

Publication Number Publication Date
EP1492744A1 EP1492744A1 (en) 2005-01-05
EP1492744B1 true EP1492744B1 (en) 2008-07-09

Family

ID=28051042

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03712015A Expired - Lifetime EP1492744B1 (en) 2002-04-03 2003-03-14 Method for colouring fertilisers

Country Status (8)

Country Link
US (1) US20050187323A1 (en)
EP (1) EP1492744B1 (en)
JP (1) JP2005527454A (en)
KR (1) KR20040091785A (en)
CN (1) CN1310849C (en)
DE (2) DE10214591A1 (en)
ES (1) ES2307910T3 (en)
WO (1) WO2003082776A1 (en)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100383089C (en) * 2005-09-01 2008-04-23 刘天暘 Coloured phosphorus ammonium fertilizer production method and its dying wrapping agent
CN1903532B (en) * 2006-08-14 2010-05-12 徐建国 Method for producing multiple color ancient-imitation wood floorings
CN103232285B (en) * 2013-04-23 2014-10-15 苏州谷力生物科技有限公司 Liquid compound fertilizer
CN105418246A (en) * 2015-12-16 2016-03-23 湖北富邦科技股份有限公司 Colorful oily fertilizer anticaking agent and application thereof
KR101879607B1 (en) * 2016-03-15 2018-07-18 이병선 Coloring agent composition for granule fertilizer and coloring method thereof
JP7026415B2 (en) * 2017-03-28 2022-02-28 ヴェルデシアン ライフ サイエンシーズ,ユー.エス.,エルエルシー Triarylmethane compounds to suppress enzyme-induced urea degradation
WO2018220577A1 (en) 2017-06-01 2018-12-06 Sabic Global Technologies B.V. Aqueous-based biodegradable coating composition
CN110128199A (en) * 2019-05-23 2019-08-16 中南林业科技大学 A kind of colour anticaking agent, preparation method and applications
CN110803953A (en) * 2019-11-06 2020-02-18 刘俐 Foliage resistance and control fertilizer for preventing heavy metal from entering edible part and application method
KR102273961B1 (en) * 2020-11-30 2021-07-06 이병선 Homogenizing Agent Composition for Granular Fertilizer and Double-Colored Granular Fertilizer
EP4116396A1 (en) * 2021-07-08 2023-01-11 Hunan Sijiu Technology Co., Ltd. Liquid candle dye and method for producing liquid candle dye
CN114249988A (en) * 2021-12-10 2022-03-29 湖北富邦新材料有限公司 Low-temperature-resistant water-based color paste for controlling color of chemical fertilizer and application thereof

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3169402D1 (en) * 1980-10-14 1985-04-25 Basf Ag Homogeneous liquid dyeing preparation
CN1092400A (en) * 1994-02-07 1994-09-21 无锡市磷肥厂 Colour high concentration composite fertilizer and technology thereof
NO300037B1 (en) * 1994-06-24 1997-03-24 Norsk Hydro As Fertilizer product and conditioner for reducing hygroscopicity and dusting to manure
DE19523464A1 (en) * 1995-06-28 1997-01-02 Basf Ag Dye preparations containing ethylene oxide-castor oil reaction products
NO305940B1 (en) * 1995-11-20 1999-08-23 Norsk Hydro As Yeast mixture having a homogeneous appearance and method of homogeneous dyeing of yeast mixture
US6099631A (en) * 1998-02-19 2000-08-08 Hitachi Koki Imaging Solutions, Inc. Ink development processes for the preparation of pigmented solid inks
US6262153B1 (en) * 1998-10-12 2001-07-17 Clariant Finance (Bvi) Limited Colored wax articles
DE10027671C2 (en) * 2000-06-03 2002-10-02 K & S Ag Coloring of mineral fertilizers
US6486248B2 (en) * 2001-01-08 2002-11-26 Milliken & Company Liquid colorant and method

Also Published As

Publication number Publication date
DE10214591A1 (en) 2003-10-16
CN1642877A (en) 2005-07-20
CN1310849C (en) 2007-04-18
ES2307910T3 (en) 2008-12-01
US20050187323A1 (en) 2005-08-25
KR20040091785A (en) 2004-10-28
JP2005527454A (en) 2005-09-15
DE50310109D1 (en) 2008-08-21
EP1492744A1 (en) 2005-01-05
WO2003082776A1 (en) 2003-10-09

Similar Documents

Publication Publication Date Title
EP1409593B1 (en) Water-based pigment dispersions, the production thereof and the use of the same
EP2013299B1 (en) Water-based pigment preparation
EP2147066B1 (en) Aqueous pigment preparations
EP1492744B1 (en) Method for colouring fertilisers
EP2183327B1 (en) Aqueous pigment preparations comprising anionic additives based on allyl ether and vinyl ether
EP2146797B1 (en) Water-based pigment preparations
EP1474484B1 (en) Granular pigment
CN1323093C (en) Solid pigment preparations containing anionic and non-ionic surface-active additives
EP2183328B1 (en) Aqueous pigment preparations having nonionic additives on the basis of alyl and vinyl ether
DE102005019747B3 (en) Aqueous pigment preparation, useful for e.g. coloring macromolecular materials, comprises organic and/or inorganic pigment and a polymer-dispersing agent
US8383749B2 (en) Dry pigment preparations comprising non-ionic additives
US8221539B2 (en) Dry pigment preparations comprising anionic additives
EP2396371B1 (en) Easy dispersible solid pigment preparations
WO2017060051A1 (en) N-alkyl glucamine-based universal pigment dispersions
CN113661197A (en) Water-based pigment preparations, their production and use
DE10244683A1 (en) Solid pigment preparations containing surface-active additives based on alkoxylated bisphenols
CN107690460A (en) A kind of decentralized waterborne general color chips
EP1160292A2 (en) Colouration of inorganic fertilisers
KR20160036539A (en) Coloring agent composition for granule fertilizer and coloring method thereof

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20041103

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

17Q First examination report despatched

Effective date: 20050112

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: CLARIANT PRODUKTE (DEUTSCHLAND) GMBH

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

RBV Designated contracting states (corrected)

Designated state(s): CH DE ES FR GB IT LI

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): CH DE ES FR GB IT LI

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 50310109

Country of ref document: DE

Date of ref document: 20080821

Kind code of ref document: P

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2307910

Country of ref document: ES

Kind code of ref document: T3

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20090219

Year of fee payment: 7

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20090414

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 20090218

Year of fee payment: 7

Ref country code: GB

Payment date: 20090302

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20090327

Year of fee payment: 7

Ref country code: IT

Payment date: 20090224

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20090216

Year of fee payment: 7

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20100314

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20101130

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100331

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20101001

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100314

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100314

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20110415

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110404

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100315